Polynitro amino dialkanoate



LYN R IN Milton B. Frankel, Pasadena, and Karl KIagei- Monrovia, Califz, assignors to Aeroj'eflGeneralCorporation, Azusa, Califi, a corporation of Ohio" n Drawing. Aprl caaun October-22,1956: Seri l- No. 617, 69;

10 Claims. crass-482 T his: invention relates to' new' compositions of? matter and a method for their preparation. In particular this invention relates to amino esters havingthe general formul wherein R is an alkyl radical. and A is an alkylene radical.

This application is a continuatiomin-part of our copending U18; patent application Serial No; 416,381, filed" wherein R and Aare as defined above.

For purposes of'convenience we'liavefound it preferablev to use an. ammonium-l salt. of ia. w'eal organic acid rather than gaseous ammonia.

The hydroxy esters used as starting materials are 'obtained by condensingfa nitronate salt of an w-geminal dinitro-containing ester with formaldehyde, as described in the J. Org. Chem., vol. 16, p. 161, 1951.

The w-geminal dinitro esters are obtained by condensing an acrylate ester with dinitro methane. After the initial ester 4,4-dinitrobutyrate is formed, the carbon chain may be lengthened by conventional methods.

In the practice of this invention, the hydroxy ester may also be produced in situ and the amino polynitro esters obtained by condensing formaldehyde with the nitronate salt of an w-geminal dinitro ester in the presence of ammonia, as illustrated in Example II.

To more clearly illustrate our invention, the following examples are presented. It is to be understood, however, that these examples are presented merely as a means of illustration and are not intended to limit the scope of the invention in any way.

EXAMPLE I Preparation of dimethyl 4,4,8,8-tetranitro-6-aza-undecanedioate' from methyl 4,4-dinitr-5-hydroxyvalerate In a 250 ml. Erlenmeyer flask was placed a solution of 30.0 gm. (0.39 mole) of ammonium acetate in 75 ml. of water and 30.0 gm. (0.135 mole) of methyl 4,4-dinitro- -hydroxyvalerate. The solution was heated on the steam bath for -15 minutes.

United States Patent On cooling a creamcolored 2,880,232 Patented Mar. 31, 19.59

2 solid separated; it was collected, washed with water and dried. The yield ofv dimethyl 4,4,8,8;-tetmnittoa6-azaundecanedioate was 25.4 gm. (88.16%)... M.P. tiff-697C; The impact stability of the compound exceeded cm./2 kg. f

EXAMPLE lI' Preparation of dimethyl 4,4,8,84etranitro-6-azamndfi canedia'atefrom sodium'sal-t o'f methyl4gf-zfi'rtitra'butyfafe' In a 5-liter 3-necked flask, fitted" with athermometer, mechanical stirrer, and dropping tunnel, was placed 500 ml. of concentrated ammonium hydroxide, 800 ml. of water, and 500 m1. of glacial acetic acid. The temperature was allowed to rise to 60-70 C. Atthis temperature a solution of 1000 gm; (equivalenfitovlfiilf or 3.97 moles of dry salt containing 15% moisture)" oftlie sodium salt of methyl 4,4-dinitrobutyrate,'2000 ml. of water, and- 324 gm. of 37% formalin was added over a period of 15 minutes. The reaction mixture was stirred at 60 C. for 1 hour; on cooling to 10 C. a solid precipitated. The product was collected, washed well with cold water, and dried in vacuo over potassium hydroxide, 480 gm. (56.8%).

We have also found that methyl 6,6-dinitro-7-hydroxyheptanoate, ethyl 5,5-dinitro-6-hydroxy-hexanoate, and propyl 3,S-dinitro-4-hydroxy-butanoate, react in a similar manner to yield the corresponding di-substituted aza compounds, namely, dimethyl 6,6,10,10-tetranitro-8-azapentadecanedioate, diethyl 5,5,9,9,-tetranitro-7-aza-tridecanedioate, and dipropyl 3,3,7,7-tetranitro-5-aza-nonancdioate.

It is apparent from the above discussion that any member' of the class of amino polynitro esters disclosed may be prepared by merely condensing an appropriate geminal dinitro hydroxy ester in the presence of ammonia. in accordance withthe teachings of this invention:

The nitro compounds of this" invention aredsft'il' as high explosives and can be used in any conventional explosive missile, projectile, rocket, or thelike, asvthe main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May: 1 7, 1949. One way-of using thehi'glf explosives of this invention in a device such as that disclosed in United States Patent No. 2,470,162, is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufliciently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The nitro compounds of our invention can also be used as ballistic modifiers for conventional demolition and blasting explosives. For example, a 50-50 mixture of a nitro compound of our invention and cellulose nitrate provides an excellent explosive which can be detonated by conventional blasting caps.

We claim:

1. As new compositions of matter, the amino polynitro esters having the general formula:

2. As a new composition of matter, dimethyl 4,4,8,8-

tetranitro-6-aza-undecanedioate having the structural and a nitronate salt of an w-geminal dinitro ester having formula: the general formula i) No: N O: H N O: CHzO Cl-UHr-CHz-('f-CH2NHOH:(fCH2CHr-C 0 CH; 6 RO-(L-Hr-A--H I. t a NO: N0: NO: method l? P Polynitro esters wherein R is a loweralkyl radical and A is a lower having the general formula: H alkylene radical. I I v 0 a N 02 NO, 0 l 5. Theimethod ofprep'aring dimethyl4,4,8,8-tetranitro- R0 IL go 0 G-aZa-undecanedioate which comprises condensing methyl 1 1 4,4-dim'tro-5-hydroxy-valerate'withammonia. v B a I I '6.-The method of cIaimI S inwhich the mmonia is introduced as ammonium acetate which comprises c ndensing ammonia with an ester hav- 7. The method of preparing dim'ethyl 4,4;8,8-tetranitroing the general formula:

15 6-aza-undecanedioate which comprises condensing the II sodium salt of methyl 4,4-dinitrobutyrate in the presence ROCTCH' AT(:J CH OH of formaldehyde and ammonia. l N0:

8. As a new composition of matter, dimethyl 6,6,10,10-

wherein R is a lower alkyl radical and A' is a lower tetranitro-S-azayentaclecanedioate having the structural NO: No, v

N O: N O: 10. As a new composition of matter, dipropyl 3,3,7,7-

tetranit'ro-5 az'a nonanedioate having the structural References Cited in the-file of this patent I UNITED STATES PATENTS 4. The method of preparing amino poly nitroe sters I having the general formula:

'NO NO 0 n." 1 ,.u. r 2,731,460 "Schenck et a1 Jan. 17, 1956 ROC-CHAC=CH:-NHCHzOA-OHz-COR 45 l/ r v I v I 1L0; 150, OTHER REFERENCES compriseszcondensing ammonia with formaldehyde Klager: 1L Org. Chem., vol: 16, pp. 161-164 (1951). 

1. AS NEW COMPOSITIONS OF MATTER, THE AMINO POLYNITRO ESTERS HAVING THE GENERAL FORMULA: 